CN1074391A - Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene - Google Patents
Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene Download PDFInfo
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- CN1074391A CN1074391A CN92100377A CN92100377A CN1074391A CN 1074391 A CN1074391 A CN 1074391A CN 92100377 A CN92100377 A CN 92100377A CN 92100377 A CN92100377 A CN 92100377A CN 1074391 A CN1074391 A CN 1074391A
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- catalyzer
- thorotrast
- calcium oxide
- barium carbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of high-efficiency methane oxidative coupling catalyst for making ethylene.Catalyzer is made up of Thorotrast, calcium oxide and barium carbonate.Wherein Thorotrast content is 28.0-91.0wt%, and calcium oxide content is 0.1-20.0wt%, and barium carbonate content is 4.5-80.0wt%.
Catalyzer provided by the invention has very high activity and selectivity, particularly has good operational stability and physical strength.Catalyzer of the present invention is made simple, good reproducibility.Over-all properties reaches the requirement of industrialized developing.
Description
The technological development field of the methane oxidation coupling system of the invention belongs to ethene.
The invention relates to a kind of by Thorotrast (ThO
2), calcium oxide (CaO) and barium carbonate (BaCO
3) the high-efficiency methane oxidative coupling catalyst for making ethylene formed.
At present, very active to the research of methane oxidation coupling catalyst for making ethylene system, because it is significant to the development and use of the major ingredient methane in the Sweet natural gas.As can be seen, although the quite a lot of element in the periodictable is attempted, most of catalyzer only are applicable to laboratory study from the result of study of having reported, its C2 hydrocarbon yield (Yc
2) and the technical indicator of aspects such as space-time yield, operational stability, physical strength also have big gap from practical application in industry.
Du Bois people such as (J.L.Dubois) is at " applied catalysis " (App.Catal.67(1) 73,1990) reported a kind of dual-component catalyst of thoriated.They with mechanical mixing and immersion process for preparing CaO-ThO
2, SrO-ThO
2, BaO-ThO
2, Ca/ThO
2, Sr/ThO
2, Ba/ThO
2, La, Sr/ThO
2, Th/CaCO
3, Th/SrCO
3And Th/La
2O
2CO
3Catalyzer.They are at methane CH
4: oxygen O
2=10: the 1(volume ratio), under the temperature of reaction T=880 ℃ of condition, estimated above-mentioned catalyzer, optimum is methane conversion XCH
4=15.1%, the selectivity Sc of C2 hydrocarbon and carbon two above hydrocarbon
2+=74.9%, the yield Yc of C2 hydrocarbon and carbon two above hydrocarbon
2+=11.3%.
Chinese patent (publication number 91110922.6) has been announced a kind of by La
2O
3, ThO
2And BaCO
3Three component catalysts that constitute.Catalyzer is estimated, at CH
4: O
2=10: the 1(volume ratio), under the temperature of reaction T=780 ℃ of condition, methane conversion XCH
4=17.0%, the selectivity Sc of C2 hydrocarbon
2=78.3%, the yield Yc of C2 hydrocarbon
2=13.3%.And at CH
4: O
2: N
2=4: 1: the 9(volume ratio), temperature of reaction T=780-900 ℃ of condition, air speed GHSV=1.0x10
4-1.2x10
5Hr
-1Down, XCH
4Can reach 30.7%, Yc
2Can reach 19.4%.Under reaction conditions, carried out operational stability test in 1000 hours, whole experimental session XCH
4, Sc
2And Yc
2Quite stable.Catalyzer has goodish physical strength.
The characteristics of oxidative coupling of methane have determined that in development and Application type catalyzer except that improving activity of such catalysts and selectivity, the operational stability of catalyzer and physical strength etc. also are the factors of very significant.
The present invention is intended to develop a kind of activity and selectivity height, operational stability and physical strength are good, the high-efficiency methane oxidative coupling catalyst that is made of Thorotrast, calcium oxide and barium carbonate.
Detailed description of the invention
Catalyzer of the present invention contains ThO
2, CaO and BaCO
3Three components, the weight percentage of each component (wt%) is:
ThO
2: 28.0-91.0wt%, preferably 44.0-75.0wt%, especially 51.5-67.0wt%.
CaO:0.1-20.0wt%, preferably 5.0-15.0wt%, especially 7.5-12.5wt%.
BaCO
3: 4.5-80.0wt%, preferably 23.4-61.1wt%, especially 33.0-51.5wt%.
Catalyzer adopts the coprecipitation method preparation.Th(NO with metering
3)
44H
2O, Ca(NO
3)
24H
2O and Ba(NO
3)
2Be dissolved in a certain amount of distilled water, make solution A.With the NH that equates with total metal ion equivalent number
4HCO
3Be dissolved in a certain amount of water, after treating to dissolve fully, add an amount of strong aqua, make the solution B of PH=10.Carry out co-precipitation with A and B.After the filtration, use the distilled water wash precipitation suitable three times one by one with the solution B volume.Dislocation is deposited in the baking oven, 140 ℃ dry 6-8 hour down, dislocation at 800-1000 ℃, preferably under 820-920 ℃, fused preferably 4-5 hour 3-6 hour in retort furnace thereafter.Grind, sieve into the particle of required order number.
Evaluating catalyst carries out in atmospheric fixed bed flowing reactive system.Reaction product is mainly C by analysis
2H
4, C
2H
6, CO
2, CO, H
2O, H
2With a small amount of high-carbon hydrocarbon.At CH
4: O
2=10: the 1(volume ratio), under the temperature of reaction T=780 ℃ of condition, methane conversion XCH
4=18.0%, the selectivity of C2 hydrocarbon and carbon three hydrocarbon is Sc
2+=79.0%.And at CH
4: O
2: N
2=4: 1: the 9(volume ratio), temperature of reaction T=780-900 ℃, air speed GHSV=1.0X10
4-1.2X10
5Hr
-1Down, XCH
4Can reach 30.7%, Yc
2+Can reach 20.1%.Catalyzer has good operational stability and physical strength after tested.
The invention provides a kind of activity and the good high-efficiency methane oxidative coupling catalyst of selectivity height, operational stability and physical strength.Catalyzer of the present invention is made simple, good reproducibility.
The present invention is further illustrated by embodiment below:
Embodiment 1.
With 7.95g Th(NO
3)
44H
2O, 0.84g Ca(NO
3)
24H
2O and 5.30g Ba(NO
3)
2Be dissolved in the 100ml distilled water and make solution A, with 4.15g NH
4HCO
3Be dissolved in the 90ml distilled water, treat to dissolve fully the back and add strong aqua adjustment solution pH value, make the solution B of PH=10 at last.Carry out co-precipitation with A and B.Filter, precipitate three times with the 100ml distilled water wash one by one.Dislocation is deposited in the baking oven, and drying is 8 hours under 140 ℃, thereafter 900 ℃ of following roastings of retort furnace 4 hours.Abrasive catalyst sieves into 30-60 order particle.Evaluating catalyst carries out reaction conditions and evaluation result such as table one in atmospheric fixed bed flowing reactive system.
Table one
CH
4:O
2:N
2T(℃) GHSV(h
-1) XCH
4Sc
2+Yc
2+
10:1:0 780 6×10
418.0 79.0 14.2
Embodiment 2.
With 7.11g Th(NO
3)
44H
2O, 2.52g Ca(NO
3)
24H
2O and 6.63g Ba(NO
3)
2Be dissolved in the 100ml distilled water and make solution A.With 4.87g NH
4HCO
3Be dissolved in the 90ml distilled water, treat to dissolve fully the back and add strong aqua adjustment solution pH value, make the solution B of PH=10 at last.Carry out co-precipitation with A and B.Filter, precipitate three times with the 100ml distilled water wash one by one.Dislocation is deposited in the baking oven, and drying is 8 hours under 140 ℃, thereafter 850 ℃ of following roastings of retort furnace 4 hours.Abrasive catalyst sieves into 30-60 order particle.Evaluating catalyst carries out reaction conditions and evaluation result such as table two in atmospheric fixed bed flowing reactive system.
Table two
CH
4:O
2:N
2T(℃) GHSV(h
-1) XCH
4SC
2+YC
2+
4:1:9 780 6×10
430.7 65.5 20.1
Embodiment 3.
Method for preparing catalyst changes Preparation of Catalyst raw material input amount and is respectively: Th(NO as example 1
3)
44H
2O 16.73g, Ca(NO
3)
24H
2O(A.R.) 1.68g, Ba(NO
3)
21.33g and NH
4HCO
35.74g.Evaluating catalyst carries out reaction conditions and evaluation result such as table three in atmospheric fixed bed flowing reactive system.
Table three
CH
4:O
2:N
2T(℃) GHSV(h
-1) XCH
4SC
2+YC
2+
4:1:9 780 6×10
431.2 64.4 20.1
4:1:9 820 6×10
432.0 64.1 20.5
Claims (7)
1, a kind of methane oxidation coupling catalyst for making ethylene, said catalyzer contains Thorotrast and barium carbonate, feature of the present invention is that said catalyzer also contains calcium oxide, Thorotrast content is 28.0-91.0wt% in the said catalyzer, calcium oxide content is 0.1-20.0wt%, and barium carbonate content is 4.5-80.0wt%.
2,, it is characterized in that Thorotrast content is 44.0-75.0wt% according to the said catalyzer of claim 1.
3,, it is characterized in that Thorotrast content is 51.5-67.0wt% according to claim 1 and 2 said catalyzer.
4,, it is characterized in that calcium oxide content is 5.0-15.0wt% according to the said catalyzer of claim 1.
5,, it is characterized in that calcium oxide content is 7.5-12.5wt% according to claim 1 and 4 said catalyzer.
6,, it is characterized in that barium carbonate content is 23.4-61.1wt% according to the said catalyzer of claim 1.
7,, it is characterized in that barium carbonate content is 33.0-51.5wt% according to claim 1 and 6 said catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100377A CN1074391A (en) | 1992-01-17 | 1992-01-17 | Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100377A CN1074391A (en) | 1992-01-17 | 1992-01-17 | Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1074391A true CN1074391A (en) | 1993-07-21 |
Family
ID=4938542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100377A Pending CN1074391A (en) | 1992-01-17 | 1992-01-17 | Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074391A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044789C (en) * | 1994-06-25 | 1999-08-25 | 厦门大学 | Catalyst for preparing carbon dihydrocarbon |
| WO2022242047A1 (en) * | 2021-05-21 | 2022-11-24 | 中国石油化工股份有限公司 | Lanthanum oxycarbonate catalyst, and preparation method therefor and application thereof |
-
1992
- 1992-01-17 CN CN92100377A patent/CN1074391A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044789C (en) * | 1994-06-25 | 1999-08-25 | 厦门大学 | Catalyst for preparing carbon dihydrocarbon |
| WO2022242047A1 (en) * | 2021-05-21 | 2022-11-24 | 中国石油化工股份有限公司 | Lanthanum oxycarbonate catalyst, and preparation method therefor and application thereof |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |